Wetting, emulsifying, and dispersing agents



, formula Patented Jan. 14, 1941 2,223,988 WETTING, EMULSIFYING, AND DISPEBSING AGENTS Melvin De Groote, University City, and .-i Keiser and Charles M. Blair, Jr., Webster Groves, Mo.,- assignors, by meme assignments, to Petrolite Corporation, Ltd, a corporation oi Delaware No Drawing. Application April 28, 193e,

SerialNo.204,852

6 Claims. ((21. 2611-404) This invention relates to new products adapted for use as wetting, dispersing or emulsifying agents. It relates more particularly to 'new ethers of partially esterified alkylolamines of the 10 in which the R's represent alkyl, aralkyl or alicyclic groups, alike or diiierent, and the X's represent alkyl; aralkyl, alicyclic, alkylol, hydroxyalicyclic, aralkylol or esterifled alkylol, aralkylol or hydroxyalicyclic groups, alike or difierent.

The various radicals may be indifierently selected, except that at least one of the radicals represented by X must contain an R4000 substituent (R4. representing methyl or the carbon linked chain of a fatty acid). The invention ineludes not only these new products, but also a new process for their preparation. The new products are quite stable and are highly eifective in acid solution.

The new ethers'of thepresent invention are advantageously produced by simple condensation of the corresponding alkylolamines, in accordance with the equation:

x x x with elimination of water between an OH group ofone molecule of the alkylolamine and an OH group of another molecule of the alkylolamlne,

with formation of an ether. of course, iimixed for a relatively long period of time, for exam-' ple, one or two days. 7 If desired, a current of through the reaction mixture to cause the reaction to proceed more rapidly.

The partially esterifiedalkylolamines used for the preparation of the new products of the present invention may be prepared in various ways. 50 In general, they may be represented by the formula . I /NRs 5 in which R1, R2 and R: are alkyl groups as herein defined, or substituted alkyl groups, which mayv bethe sameor different, at least one of which has at least one RQCOO stituent (R4 representing methyl or the carbon linked chain 5. of a fatty acid) and at least one of which has at least one. 03' (alcoholic hydroiwl) substituent, compounds having an R4600 substltuent and an OH substituent in the same substituted alkyl group, with the other alkyl groups substituted 10 or unsubstituted, being included. The new products may be prepared by heating such a par- ,well as the substituted acids which may occur in a natural fats or oils, such as ricinoleic acid, and modifications of the acids which occur in natural oils, such as those in blown or bodied oils; and the term higher fatty acid is used to des- 3. ignate those carboxylic acids, generally having at least eight carbonatoms, which occur combined with glycerin in natural oils and fats. It is understood that the term alkylolamine and alkyl are used conventionally in chemistry to .refer to paraffin compounds which are non-cyclic and aliphatic in nature. We have found, however, that the alicyclic and hydroxyalicyclic,

as well as the aralkyl and aralkylol amines are with respect to the reactions involved in the var- 40 ious phases of the present invention, similar to the corresponding alkyl and alkylol amines with the limitation that the aralkyl and aralkylol com-' inert gas, such as dry nitrogen, may be passed pounds have the linkage to the nitrogen atom in the side chain. For this reason, for the purpose of describing the present invention only, it is understood that the terms alky and alkylol" include within their scope alicyclic, aralkyl, hydroxyalicyclic and-aralkylol groups.

One advantageous method of preparing the partially esterifled alkylolamines is that described in our application. Serial No. 180,993, flied Dealcoholic hydroxyl, the proportions of the ester and the alkylolamine being such that after the replacement of the glycerin or other alcohol of the fatty acid ester used, there will be at least one free alcoholic hydroxyl in the esterifled alkylolamines. Such alkylolamineahaving at least one esterifled hydroxyl group and at least one free hydroxyl group, are herein referred to as partially esterifled alkylolaniines." The free alcoholic hydroxyl of the partially esterified alkylolamine is available for condensation with a corresponding hydroxyl group of another molecule of the amine, or a corresponding hydroxyl group of another alkylolamine, to produce ethereal reaction products. However, the preparation of the partially esterified aikylolamines which may be used is not limited to the procedure described in said prior application, as they may also be prepared by suitable reaction between an acyl halide, such as an acyl chloride, and a tertiary alkylolamine, or in other ways. Also, it is to be understood that the alkylolamines used in accordance with the present invention need not be esters of tertiary alkylolamines with the higher fatty acids, but include tertiary alkylolamines partially esterifled with the lower fatty acids, such as acetic acid, propionic acid, butyric acid, etc.

Among the amines which may be partially esterified for use in the production of the new products of the present invention are a wide range of tertiary alkylol and tertiary alkylalisylolamines. The two essentials are that the alkylolamine contain at least two alcoholic hydroxyl groups, which may be attached to the same or different carbon chains, and be a tertiary amine, that is, with three alkyl or alkylol groups linked to carbon atoms to the nitrogen atom.

Included among the suitable amines are triethanolamine, diethanolalkylamines, such as diethanolethylamine diethanolpropylamine, etc., tertiary glyceryl amines, such as tridihydroxy propylamine, dihydroxypropyldialkylamines, such as dihydroxypropyldiethylamine, di-dihydroxypropylalkylamines, diethanolmethylamine, tri- -propanolamine, dipropanolmethylamine, cyclohexanoldiethanolamine, di-cyclohexanolethylamine, etc. All such products may be readily prepared by known processes, and all of them are tertiary amines having at least two alcoholic hydroxyl groups, thus being adapted to form esters with higher fatty acids, such esters having at least one free hydroxyl group. Typical of the amines which may be used are the following:

'(cmlomm 'lriethanolamine (ClH|oH)-N rHB) Diethenolethyiamiue (CRHAOH) (C|H|OH)N C Diethanolmethylamine i z a(0H):]aN

Tri-d ih ydroxypropylemine (trlglycerylamine) [CaHKO h] [Ca KQ hY-N (dim) r dbl-dihydroxypropylethylamine (diglycerylethylamine) mono-fatty acid ester.

l a iaw hi (CaHQ-N (01m) Dihydroxypropyldiethylamine (glyceryl (iiethylarninc) (CaHiOHhN Tripropsnolamine (CX oOH) (CaH0H)-N Dipropanolethylamine [CSH5(OQH5)OH] i sHi(Ct t) OH]-N alls) Di-phonylpropanolethylamine (CaHcOID-N (COHWOH) Cyclohexanoldiethanolamine (CeHicQ eHioO H)N zHs) Dicyclohexanolethylamiue (C H OH)zN Tributanolamine (CIHBOH) (C|HsOH)-N ((izHrOH) Dibutanolethanolamine lHBO (CHaOH)N Dibutanolmethylamine Any of these aminesmay be partially esterified with a suitable fatty acid or fatty acids, by the procedure described in our said application Serial No. 180,993, or by other methods. In the case of such alkylolamines as diethanolmethylamine,

having but two alcoholic hydroxyl groups, the esterification should be such as to produce the groups, such as triethalonamine, triglycerylamine, etc., the esteriflcation may be such as to produce mono-fatty acid esters, di-fatty. acid esters, or

least one free alcoholic hydroxyl remains avail/- able for condensation to form the new ethers. The fatty acids used for the esterification may either be the lower fatty acids, such as acetic acid, propionic acid, butyric acid, etc., or the higher fatty acids, such as occur naturally combined with glycerin as triglycerides, including those In thecase oi alkyloi-' amines having three or more alcoholic hydroxyl even more highly esterified products, providing at which occur combined with glycerin in such vegetable oils as cocoanut and palm-kernel oil, olive oil, castor oil, palm oil, peanut oil, the drying and semi-drying oils such as corn oil, rape-seed oil, soya bean oil, sunflower seed oil, linseed oil, perilla oil, etc., as well as the animal and marine oils, such as tallow, sardine oil, menhaden oil, etc., and the blown or bodied oils, such as blown castor oil, blown rapeseed oil or perille. oil, bodied linseed oil, etc. The fatty acids derived from blown or bodied oils have characteristics someence of oxygen in the long carbon-linked chain characteristic of castor oil fatty acids. In general, tertiary alkylolamines partially esterifled with any of these fatty acids may be advantageously converted into ethers to form new ethereal products having important advantages as wetting, emulsifying and dispersing agents.

The invention will be further illustrated by the following specific examples, but it is not limited thereto.

Example 1.-Cornmercial triethanolamine and cocoanut oil, in the proportions of 1 mole of cocoanut oil to 3 moles of trlethanolamine are heated to a temperature between about 150C.

and 180 C. for a period of about two days. I If desired, a current of inert gas, such as dry nitrogen, may be passed through the reaction mixture to speed up the reaction. The resulting product consists mainly of the ether formed by the elimination of a molecule of water from two molecules of the mono-fatty acid ester of triethanolamine, with minor proportions of more complex ethers, ethers of the di-fatty acid ester of triethanolamine. ethers of the fatty acid esters of triethanolamine with glycerin or monoor di-glycerides etc. The product has good wetting, emulsifying and detergent properties.

Example 2.--The'di-ricino1eic acid ester of triglycerylam'ine is heated to a temperature between about 150 C. and 180 C. for about two days.

with the production of a product consisting mainly of ethers such as, di-dihydroxypropyl mono-hydroxypropylamine di-ricinoleate ether,

and more complex ethers formed by the condensation of more than two molecules of the triglycerylamine di-ricinoleate, etc.

Example 3.-'-Diethan01ethylamine monoacetate is heated to a temperature between about 150 C. and 180 C. for about two days with the production of a product consisting mainly of the ether of the formula:

cmcooour. olmooccm -CzH4O.CH -N In place of the partially esterifled alkylolamamines referred to above, may be used, with the production of corresponding ethers. The new ethers include the more or less simple ethers formed by the condensation of two molecules of the partially esterified alkylolamines, and more complex ethereal derivatives which may be formed by the condensation of more than two molecules of the partially esterifled alkylolamines together. The invention also includes the ethereal reaction products produced by heating a partially esterified alkylolamine with other tertiary alkylolamines, including other partially esterifled tertiary alkylolamines or simple'tertiary alkylolamines, whether having but one hydroxy group or more than one hydroxy group, as illustrated in the followingexample.

Example 4.The mono-fatty'acid ester of triethanolamine obtained by heating triethanolamine with cocoanut oil, as described in our application Serial No. 180,993, is heated with diethylethanolamine for about two days at a temperature of from 150 C. to-180 C., with ehmination of water and condensation to form triethylamine ethyldiethanolamine stearate ether.

The new ethereal products of the present invention may also be prepared by other processes involving the reaction of the starting materials in a different order. For example, ethers may be prepared by heating a suitable alkylolamine or mixture of alkylolamines at a temperature sufflciently high to bring about ether formation for a period sufiicient to bring about etheriflcation without removal of all of the alcoholic hydrox'yl groups. The resulting ethers, haying free hydroxyl groups, may then be reacted with a fatty acid, fatty oil, acyl halide, or the like to produce esterifled or partially esterified iii-alkylolaminoaligrl others, or more complex ethers. This procedure is illustrated by the following example.

Example 5.-Four moles of commercial triethanolamine are heated to a temperature of be tween about 180 C. and 200 C. for several hours,

or until about 2 moles of water have been evolved from the mixture. If desired, a small amount of a dehydration catalyst, such as sodium hydroxide, sodium carbonate, etc., may be added to the reaction mass to increase the rate of reaction. The product, contains a substantial proportion of the ether of the formula:

Hoom. canon One mole of commercial cocoanut oil is then added tothe above reaction mass, and heating is continued at a temperature between about C. and C. for three or four hours. The resulting final product is similar to that obtained by the process of Example 1.

We claim: i

' 1. The process of preparing products adapted for use as wetting, emulsifying and dispersing agents, which comprises heating a tertiary alkylolamine partially esterifled with a fatty acid with a tertiary alkylolamine to a temperature of time suillcient to effect condensation with the production of a reaction product having an ether linkage.

3. The-process as in claim 1 in which a. current of inert gas is passed through the reaction mixture. r

4. Compounds of theformula and the carbon linked chains of fatty acids.

5. Compounds of the formula 6. Compounds of the formula ZOCIHA I (h RCOQCQH; clHlOOCR -C:H4OC;H4 -CsHu-Q-CrIL-N g I 6 Yocna'. w e cmmn in which R represents the long carbon linked in which Y represents radicals indifierently sechain characteristic of the higher fatty acids. lected from the class consisting of hydrogen and GTE. aliphatic carboxylic acyl radicals and Z reprem sents an aliphatic carboxylicacyl group. v CHARLES M. BLAIR, JR. m 

